Cationic copolymerization of phenyl glycidyl ether with lactones. Characterization of the reaction mixture with chromatographic methods

Abstract

This paper refers to the influence of the catalysts boron trifluoride p‐methoxyaniline complex (BF3 · MA) and boron trifluoride etherate complex (BF3 · Et2O) having different reactivity in cationic copolymerization of phenyl glycidyl ether (PGE) with γ‐butyrolactone (γ‐BL) and ϵ‐caprolactone (ϵ‐CL), respectively. Reactions were followed by FT‐IR, HPLC and SEC. SEC with multiple detection and Two‐Dimensional‐Chromatography HPLC/SEC were used to characterize the products in view to their copolymer compositions. In the presence of BF3 · MA a preferred formation of spiroorthoesters (SOE) was observed; the polymerization of SOE under these conditions can be neglected. In case of the more reactive BF3 · Et2O the epoxide homopolymerization strongly competes with SOE formation, resulting in a product mixture of epoxide homopolymers (and in the case of ϵ‐CL also lactone homopolymers) and copolymers with low lactone content.

Microwave‐Accelerated Polymerization of 2‐Phenoxymethyl‐1,4,6‐trioxaspiro[4,4]nonane with Diglycidyl Ether of Bisphenol A

“…Some kinds of bicyclic monomers such as spiroorthoesters (SOEs), spiroorthocarbonates (SOCs) and bicycloorthoesters (BOEs) have been reported to maintain their volume or actually expand during the double ring-opening polymerization. [7][8][9][10] SOEs can be readily synthesized from epoxides and lactones [11,12] and undergo cationic…”

Copolymerization of diglycidyl ether of bisphenol A with γ‐butyrolactone catalyzed by ytterbium triflate: Shrinkage during curing

“…Because SOEs can readily be synthesized from lactones and epoxides,9, 10 it has been proposed that three‐dimensional networks be prepared by the copolymerization of epoxy resins and lactones, which can form an intermediate SOE, reducing the volume shrinkage during curing.…”

Anionic alternating copolymerization of epoxide and 3,4‐dihydrocoumarin and its application to networked polymers

“…Another important but insufficiently investigated aspect of lactones is their ability to copolymerize with epoxides. Although a few aliphatic lactones have been employed for the purpose of controlling initial viscosity and curing kinetics of some practical epoxy formulations, the potential of lactones as comonomers has not been fully exploited due to the lack of detailed molecular designs of lactone‐type comonomers with investigation of their copolymerization behaviors 10–12. In addition to the intrinsic thermodynamic parameters such as enthalpy and entropy in ring‐opening reactions of lactones, the reactivity of the resulting chain‐end species is a critical factor in determining copolymerization kinetics and natures involving random, block and alternating copolymers, on which the properties of the resulting copolymers strongly depend.…”